EP1984424B1 - Copolymeren enthaltend polyamid- und polyetherblocken, mit verbesserten mechanischen eigenschaften - Google Patents

Copolymeren enthaltend polyamid- und polyetherblocken, mit verbesserten mechanischen eigenschaften Download PDF

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Publication number
EP1984424B1
EP1984424B1 EP07731638.8A EP07731638A EP1984424B1 EP 1984424 B1 EP1984424 B1 EP 1984424B1 EP 07731638 A EP07731638 A EP 07731638A EP 1984424 B1 EP1984424 B1 EP 1984424B1
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Prior art keywords
blocks
copolymer
pax
ptmg
polyether
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French (fr)
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EP1984424A2 (de
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Frédéric MALET
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Arkema France SA
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Arkema France SA
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/40—Polyamides containing oxygen in the form of ether groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/44—Polyester-amides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
    • C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
    • Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
    • Y10T428/139—Open-ended, self-supporting conduit, cylinder, or tube-type article
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/249921—Web or sheet containing structurally defined element or component

Definitions

  • the present invention relates to novel copolymers comprising polyamide blocks (abbreviated PA block) and polyether blocks (abbreviated PE block) having improved optical and / or mechanical properties.
  • polyamide blocks abbreviated PA block
  • PE block polyether blocks
  • Such block copolymers are also called polyether block amides (abbreviation PEBA).
  • the PEBA copolymers of the invention belong to the particular class of polyetheresteramides when they result from the copolycondensation of polyamide sequences with reactive carboxyl ends with polyether sequences with reactive ends, which are polyether polyols (polyetherdiols), the bonds between the polyamide blocks. and the polyether blocks being ester bonds or to the class of polyetheramides when the polyether blocks are amine terminated.
  • the document EP1500684 discloses antistatic elastomeric compositions comprising a PEBA copolymer comprising essentially PE PE blocks and PAX.Y blocks with X an aliphatic diamine such as hexamethylenediamine and C9 to C25 diamines and Y a C9 aliphatic diacid with C25. These copolymers with antistatic properties are not within the scope of our invention and are, of course, excluded as such.
  • the document EP1262527 relates to a composition of antistatic polymers comprising a PEBA PAX.Y type with as aliphatic diamine X: hexamethylenediamine, dodecamethylenediamine and trimethylhexamethylenediamine and as aliphatic diacid Y: butanoic, adipic, azelaic, suberic, sebacic, dodecanedicarboxylic, dimerized fatty acids and alpha, omega diacid polyoxyalkylenes.
  • the PEG PE blocks imparting the antistatic properties to the copolymer and the composition, can be used with PPG blocks or with PTMG blocks. These copolymers are not within the scope of our invention and are, of course, excluded as such.
  • the document WO03 / 050159 discloses PEBAs having as a hard segment a PAX.Y block with X a linear aliphatic diamine containing 4-14 carbon atoms and Y a linear aliphatic diacid containing from 4 to 14 carbon atoms and with PO3G as a soft segment, the latter may comprise up to 60% by weight of another polyether such as PEG, PPG and PTMG. These copolymers are not within the scope of our invention and are, of course, excluded as such.
  • the document WO04 / 037898 relates to a block copolymer PA and PE blocks whose PA blocks are copolyamides which may be of the PAX1.Y1 / X2.Y2 or PAX1.Y1 / Z type, where X1 and X2 are diamines, Y1 and Y2 being diacids and Z being a lactam or an amino acid.
  • PA and PE blocks whose PA blocks are copolyamides which may be of the PAX1.Y1 / X2.Y2 or PAX1.Y1 / Z type, where X1 and X2 are diamines, Y1 and Y2 being diacids and Z being a lactam or an amino acid.
  • the applicant company has surprisingly discovered a new class of PEBA with improved optical properties, in particular a decrease in PEBA opacity and / or improved mechanical properties, in particular a very good resistance to dynamic fatigue.
  • dicarboxylic acids having Y carbon atoms there may be mentioned sebacic acid, dodecanedicarboxylic acid, octadecanedicarboxylic acid;
  • linear aliphatic diamines having X carbon atoms mention may be made of tetramethylene diamine, hexamethylenediamine and 1,10-decamethylenediamine.
  • the polyether blocks of the PEBA copolymer of the invention are advantageously derived from at least one polyalkylene ether polyol, in particular a polyalkylene ether diol and more particularly chosen from polypropylene glycol (PPG), polytetramethylene glycol (PTMG), their mixtures and their copolymers.
  • PPG polypropylene glycol
  • PTMG polytetramethylene glycol
  • the PTMG will be selected.
  • the PE blocks may comprise a mixture of PE blocks or be a polyether copolymer. In this case, they comprise 0-39% by weight of PO3G and / or PEG and 100-61%, by weight of polyether (s) different (s) PO3G or PEG, (weight relative to the weight of the blocks PE).
  • the PE blocks are never the majority in PEG and never comprise more than 39% by weight of PO3G (weight relative to the weight of PE blocks).
  • the copolymer is characterized in that the 100 to 61% of polyether in (iii) are chosen from PTMG, PPG, their mixtures and their copolymers.
  • the polyether blocks of the PEBA copolymer according to the present invention can also be polyoxyalkylene sequences with NH 2 chain ends, such sequences being obtainable by cyanoacetylation of aliphatic dihydroxy aliphatic polyoxyalkylene aliphatic sequences known as polyetherdiols. More particularly, it is possible to use Jeffamines (for example Jeffamine® D400, D2000, ED 2003, XTJ 542, commercial products from Huntsman.) See also patents JP 2004346274 , JP 2004352794 and EP1482011 ).
  • the number-average molecular weight of a copolymer according to the present invention is advantageously between 5000 and 50000, preferably between 10000 and 30000.
  • the number-average molecular mass of the PA blocks is advantageously between 500 and 10,000, preferably between 600 and 7,000, more advantageously between 1,500 and 6,000.
  • the number-average molecular mass of the PE blocks is advantageously between 250 and 5000, preferably between 250 and 2000, and even more advantageously between 350 and 1000.
  • the PA blocks advantageously represent between 5 and 95, preferably between 10 and 95% by weight of the sum of the PA blocks and the PE blocks of the copolymer of the present invention.
  • the general two-step preparation method of the PEBA copolymers of the invention having ester bonds between PA blocks and PE blocks is known and is described, for example, in the French patent. FR 2,846,332 .
  • the general method for preparing the PEBA copolymers of the invention having amide linkages between PA blocks and PE blocks is known and described, for example in the European patent. EP 1 482 011 .
  • the formation reaction of the PA block is usually between 180 and 300 ° C, preferably 200 to 290 ° C, the pressure in the reactor is between 5 and 30 bar, and is maintained for about 2 to 3 hours. The pressure is slowly reduced by putting the reactor under pressure atmospheric, then excess water is distilled for example for an hour or two.
  • the carboxylic acid terminated polyamide having been prepared, the polyether and a catalyst are then added.
  • the polyether can be added in one or more times, as can the catalyst.
  • the polyether is first added, the reaction of the OH ends of the polyether and the COOH ends of the polyamide begins with the formation of ester bonds and elimination of water. As much water as possible is removed from the reaction medium by distillation, and then the catalyst is introduced to complete the bonding of the polyamide blocks and the polyether blocks.
  • This second step is carried out with stirring, preferably under a vacuum of at least 6 mmHg (800 Pa) at a temperature such that the reagents and copolymers obtained are in the molten state.
  • this temperature can be between 100 and 400 ° C and most often 200 and 300 ° C.
  • the reaction is monitored by measuring the torque exerted by the molten polymer on the stirrer or by measuring the electrical power consumed by the stirrer. The end of the reaction is determined by the value of the target torque or power.
  • the present invention also relates to a shaped article, which can be advantageously transparent or translucent, such as for example fiber, fabric, film, sheet, ring, tube, any injected part (shoe sole parts, etc %) comprising copolymers as defined above.
  • a PEBA was prepared from PA 6.18 blocks of molar mass 2000 g / mol and PTMG blocks of molar mass 1000 g / mol according to the following procedure: The following monomers are introduced into an autoclave equipped with a stirrer so as to obtain 6.18 PA blocks: 5 kg of hexamethylene diamine, 16.9 kg of octadecanedioic acid. The mixture thus formed is put under an inert atmosphere and heated until the temperature reaches 250 ° C and 32 bar pressure. After a hold of 1h, then performs a relaxation operation of 1h to return to atmospheric pressure.
  • the polytetramethylene glycol of mass 1000 g / mol (10.22 kg) and Zr (OBu) 4 (30 g) are then added to the reactor to complete the polymerization at 240 ° C. under an absolute pressure of 8 mbar (800 Pa).
  • the final product PA 6.18-PTMG has an inherent viscosity of 1.4 dl / g.
  • a PEBA was prepared from PA blocks 10.14 of molar mass 5000 g / mol and PTMG blocks of molar mass 650 g / mol according to the preceding procedure with, however, as diamine 1,10-decamethylenediamine (11.95 kg) 1,12-dodecane dicarboxylic acid (19.4 kg) and polytetramethylene glycol (3.7 kg) as diacid.
  • the final product PA 10.14-PTMG has an inherent viscosity of 1.28 dl / g.
  • Injection molding of 100 * 100 * 2 mm plates confirms the improved optical properties of the product with transmission at 460 nm of 49.5%, 560 nm of 62.9% and 700 nm of 71.7% (measurements made according to ASTM D 1003), an opacity of approximately 20% (measured according to ASTM D 1003) and a haze of 11 (measured according to ISO 2814), which can be compared to the values obtained for a copolymer of the same size of PA blocks and of the same PE block size respectively but based on PA 12 and PTMG, said values being respectively 14, 23, 35, unmeasured and 25.
  • the thermal properties in particular the melting point of the PA phase, may be higher than in the case of a PA 12 / PTMG copolymer and this, for the same molar mass of the PA block and the PE block.
  • a PEBA 6.14 / PTMG copolymer with a PA 6.14 block having a mass of 5000 g / mol and a PTMG block of 650 g / mol has a melting point of 196-206 ° C.
  • a PEBA copolymer of PA12 type / PTMG of the same block size has a melting point of 172 ° C.
  • a PEBA was prepared from PA 6.14 blocks of molar mass 5000 g / mol and PTMG blocks of molar mass 650 g / mol according to the preceding procedure with, however, as diamine 1,6-hexamethylenediamine (13.2 kg). as diacid 1,12-dodecane dicarboxylic acid (31.6 kg) and polytetramethylene glycol (5.3 kg).
  • the final product PA 6.14-PTMG has an inherent viscosity of 1.44 dl / g. The bending modulus of the product thus obtained (after conditioning for 14 days at 23 ° C.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyamides (AREA)
  • Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)

Claims (13)

  1. Copolymer PAX.Y/PE, umfassend Blöcke von Polyamid PA alternierend mit Blöcken von Polyether PE, wobei die Blöcke PA aus Blöcken von Homopolyamid PA X.Y bestehen, erhalten durch Polykondensation
    - eines linearen aliphatischen Diamins mit X Kohlenstoffatomen;
    - einer Dicarbonsäure mit Y Kohlenstoffatomen, ausgewählt aus linearen aliphatischen Disäuren;
    wobei das Copolymer dadurch gekennzeichnet ist, dass:
    - die Blöcke PA Carboxyltermini aufweisen;
    - X mindestens gleich 4 ist, vorzugsweise mindestens gleich 6;
    - Y mindestens gleich 10 ist, vorzugsweise mindestens gleich 12;
    - die Blöcke PE:
    (i) entweder vorzugsweise Blöcke PE mit Hydroxyltermini, anders genannt Blöcke von PE-Diolen, derart sind, dass die Bindungen zwischen den Blöcken PA mit Carboxyltermini und den Blöcken von PE-Diolen Esterbindungen sind;
    (ii) oder vorzugsweise Blöcke PE mit NH2-Termini, in dem Fall, wo Y eine Anzahl von Kohlenstoffatomen größer als 14 aufweist, derart sind, dass die Bindungen zwischen den Blöcken PA mit Carboxytermini und den Blöcken PE mit NH2-Termini Amidbindungen sind;
    (iii) umfassend 0 bis 39 Gew.-% PO3G und/oder PEG und 100 bis 61 Gew.-% Polyether, verschieden von PO3G oder von PEG (Gew.-% ausgedrückt bezogen auf das Gesamtgewicht des Copolymers);
    dadurch gekennzeichnet, dass (iv) die Kristallinität des Blocks PAX.Y > ist als die Kristallinität eines Blocks PA12 mit derselben Größe und/oder (v) die Trennung der Phase PA/PE des Copolymers PAX.Y/PE > ist als jene eines Copolymers PA12/PTMG, bestehend aus Blöcken von PA12 mit derselben Größe wie die Blöcke PA X.Y des Copolymers PAX.Y/PE und aus Blöcken von PTMG mit derselben Größe wie die Blöcke PE des Copolymers PAX.Y/PE,
    dadurch gekennzeichnet, dass X + Y = 24 bei den Blöcken PA von PA10.14 oder von PA6.18, oder dadurch, dass X + Y = 22 bei den Blöcken PA von PA10.12, oder dadurch, dass X + Y = 20 bei den Blöcken PA von PA6.14 oder von PA10.10.
  2. Copolymer nach Anspruch 1, dadurch gekennzeichnet, dass die 100 bis 61 % Polyether in (iii) ausgewählt sind aus PTMG, PPG oder ihren Mischungen, wobei der Polyether vorzugsweise PTMG ist.
  3. Copolymer nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass die zahlenmittlere Molekularmasse der Blöcke PA zwischen 500 und 10000, vorzugsweise zwischen 600 und 7000, noch vorteilhafter zwischen 1500 und 6000, beträgt.
  4. Copolymer nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass die zahlenmittlere Molekularmasse der Blöcke PE zwischen 250 und 5000, vorzugsweise zwischen 250 und 2000, noch vorteilhafter zwischen 350 und 1000, beträgt.
  5. Copolymer nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass die zahlenmittlere Molekularmasse des Copolymers zwischen 5000 und 50000, vorzugsweise zwischen 10000 und 30000, beträgt.
  6. Copolymer nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass die Blöcke PA vorteilhaft zwischen 5 und 95 Gew.-%, vorzugsweise zwischen 10 und 95 Gew.-%, der Summe der Blöcke PA und der Blöcke PE des Copolymers darstellen.
  7. Verfahren zur Herstellung eines Copolymers, wie in einem der vorhergehenden Ansprüche definiert, dadurch gekennzeichnet, dass:
    - in einem ersten Schritt Blöcke von Polyamid PA hergestellt werden durch Polykondensation
    ∘ eines linearen aliphatischen Diamins mit X Kohlenstoffatomen;
    ∘ einer Disäure, ausgewählt aus Dicarbonsäuren mit Y Kohlenstoffatomen; und
    ∘ in Anwesenheit eines Kettenreglers, ausgewählt aus Dicarbonsäuren; anschließend
    - in einem zweiten Schritt die erhaltenen Blöcke von Polyamid PA mit Blöcken von Polyether PE in Anwesenheit eines Katalysators umgesetzt werden.
  8. Verfahren zur Herstellung eines Copolymers, wie in einem der Ansprüche 1 bis 6 definiert, dadurch gekennzeichnet, dass eine Polykondensation durchgeführt wird in einem Schritt
    - eines linearen aliphatischen Diamins mit X Kohlenstoffatomen;
    - in Anwesenheit eines Kettenreglers, ausgewählt aus Dicarbonsäuren;
    - in Anwesenheit von Blöcken von Polyether PE; und
    - in Anwesenheit eines Katalysators für die Reaktion zwischen den Böcken PE und den Blöcken PA.
  9. Herstellungsverfahren nach einem der Ansprüche 7 und 8, dadurch gekennzeichnet, dass als Kettenregler eine Dicarbonsäure mit Y Kohlenstoffatomen verwendet wird, die im Überschuss in Bezug auf die Stöchiometrie des Diamins eingebracht wird.
  10. Herstellungsverfahren nach einem der Ansprüche 7 bis 9, dadurch gekennzeichnet, dass als Katalysator ein Derivat eines Metalls, ausgewählt aus der Gruppe gebildet von Titan, Zirconium und Hafnium, oder eine starke Säure, wie Phosphorsäure oder Borsäure, verwendet wird.
  11. Herstellungsverfahren nach einem der Ansprüche 7 bis 10, dadurch gekennzeichnet, dass die Polykondensation bei einer Temperatur von 180 bis 300°C durchgeführt wird.
  12. Formkörper, wie eine Faser, ein Gewebe, ein Film, eine Folie, ein Ring, ein Rohr, ein Spritzgussteil, beispielsweise ein Teil einer Schuhsohle, umfassend das Copolymer, wie in einem der Ansprüche 1 bis 6 definiert.
  13. Verwendung eines Copolymers PAX.Y/PE nach einem der Ansprüche 1 bis 6, zur Herstellung eines Objekts, dessen mechanische Eigenschaften in Bezug auf das gleiche Objekt verbessert sind, das mit einem Copolymer mit Blöcken PA von PA12 und mit Blöcken PE von PTMG hergestellt ist, mit der Maßgabe, dass:
    - die Größe der Blöcke PA der Copolymere PAX.Y/PE und PA12/PTMG gleich oder im Wesentlichen gleich ist und die Größe der Blöcke PE der Copolymere PAX.Y/PE und PA12/PTMG gleich oder im Wesentlichen gleich ist; und/oder
    - die Kristallinität des Blocks PAX.Y > ist als die Kristallinität eines Blocks PA12 mit derselben Größe und/oder die Trennung der Phase PA/PE des Copolymers PAX.Y/PE > ist als jene eines Copolymers PA12/PTMG, bestehend aus Blöcken von PA12 mit derselben Größe wie die Blöcke PA X.Y des Copolymers PAX.Y/PE und aus Blöcken von PTMG mit derselben Größe wie die Blöcke PE des Copolymers PAX.Y/PE.
EP07731638.8A 2006-02-16 2007-02-16 Copolymeren enthaltend polyamid- und polyetherblocken, mit verbesserten mechanischen eigenschaften Active EP1984424B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR0601355A FR2897355B1 (fr) 2006-02-16 2006-02-16 Copolymeres comportant des blocs polyamide et des blocs polyether, ayant des proprietes optiques et thermiques ameliorees
US78435006P 2006-03-21 2006-03-21
PCT/FR2007/050813 WO2007093750A2 (fr) 2006-02-16 2007-02-16 Copolymeres comportant des blocs polyamide et des blocs polyether, ayant des proprietes mecaniques ameliorees

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EP1984424A2 EP1984424A2 (de) 2008-10-29
EP1984424B1 true EP1984424B1 (de) 2018-05-16

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EP07731639A Withdrawn EP1984425A2 (de) 2006-02-16 2007-02-16 Copolymere mit polyamidblöcken und polyetherblöcken sowie verbesserten optischen eigenschaften
EP07731638.8A Active EP1984424B1 (de) 2006-02-16 2007-02-16 Copolymeren enthaltend polyamid- und polyetherblocken, mit verbesserten mechanischen eigenschaften

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US (5) US20090017246A1 (de)
EP (2) EP1984425A2 (de)
JP (2) JP5117408B2 (de)
KR (2) KR20080093044A (de)
CN (2) CN101426834B (de)
CA (2) CA2641931A1 (de)
FR (1) FR2897355B1 (de)
TW (2) TW200745219A (de)
WO (2) WO2007093751A2 (de)

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CN110041521B (zh) * 2019-05-15 2021-05-11 洛阳理工学院 一种压电聚合物及其制备方法
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EP3805291A1 (de) 2019-10-11 2021-04-14 Evonik Operations GmbH Formmasse enthaltend polyetheramid (pea)
CN110903477A (zh) * 2019-12-20 2020-03-24 山东安岩新材料科技有限公司 一种混合二胺改性长碳链尼龙及其制备方法
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CN118215703A (zh) * 2021-11-10 2024-06-18 奥升德功能材料运营有限公司 通过引入聚醚二胺改进聚酰胺的干态和低温性能
CN116751355B (zh) * 2023-08-17 2023-11-03 成都上泰科技有限公司 一种动力电池软包铝塑膜用有机硅改性聚氨酯高聚物及其制备方法

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CN101426833A (zh) 2009-05-06
US20120065340A1 (en) 2012-03-15
US20090023868A1 (en) 2009-01-22
US20120043676A1 (en) 2012-02-23
US20090017246A1 (en) 2009-01-15
EP1984424A2 (de) 2008-10-29
CN101426834A (zh) 2009-05-06
KR20080093044A (ko) 2008-10-17
US8889822B2 (en) 2014-11-18
KR20080093050A (ko) 2008-10-17
WO2007093751A3 (fr) 2007-10-11
JP2009526890A (ja) 2009-07-23
WO2007093751A2 (fr) 2007-08-23
TW200745219A (en) 2007-12-16
EP1984425A2 (de) 2008-10-29
US20130296502A1 (en) 2013-11-07
JP5117408B2 (ja) 2013-01-16
JP5260319B2 (ja) 2013-08-14
CN101426833B (zh) 2012-11-21
FR2897355B1 (fr) 2012-07-20
WO2007093750A3 (fr) 2007-10-11
CA2641931A1 (fr) 2007-08-23
WO2007093750A2 (fr) 2007-08-23
JP2009526891A (ja) 2009-07-23
FR2897355A1 (fr) 2007-08-17
TW200745220A (en) 2007-12-16
CN101426834B (zh) 2012-04-18
CA2641932A1 (fr) 2007-08-23

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